Process of converting higher-boiling petroleum hydrocarbons into lowerboiling petroleum hydrocarbons



' 1927. March c. B. BUERGER PROCESS OF CONVERTING HIGHER BOILINGPETROLEUM HYDROCARBONS INTO LOWER BOILING PETROLEUM HYDROCARBONS FiledJuly 22. 1925 3 Sheets-Sheet 1 m m a 7m 7 M u arch c. B. BUERGER PROCESSOF CONVERTING HIGHER BOILING PETROLEUM HYDROCARBONS INTO LOWER BOILINGPETROLEUM HYDROCARBONS Filed July 22, 1925 3 Sheets-Sheet 2 gwuentoc1927. 1,623,025 March c. B. BUERGER PROCESS OF CONVERTING HIGHER BOILINGPETROLEUM HYDROCARBONS INTO LOWER BOILING PETROLEUM HYDROCARBONS I FiledJuly 22, 1925 3 Sheets-Sheet 3 ff "h rzy. $51,

Patented ll/lar. 29,1927. p I r V 1523,4125

UNITED STATES PATENT O'F FIC E.

CHARLES IB. BUERGER OF PITTSBURGH, PENNSYLVANIA, ASSIGNOR TO GULF REFINING COMPANY, OFYPITTSBURGH, PENNSYLVANIA, A CORPORATION OF TEXAS.

PROCESS OF CONVERTING HIGHER-BOILING PETROLEUM HYDROCARBONS INTO LOWER-BOILING PETROLEUM HYDROGARBONS.

Application filed July 22, 1925 Serial No. 45,330.

This inventionrelates to processesof conaluminum chlorid used is usuallymade 65 verting higher boiling petroleum hydrofrom bauxite whichcontains small proporcarbons into lower boiling petroleum hydrotions oftitanium oxid, silicon oxid, iron carbons and it comprises distillingthe oxid, etc, so that it is not pure but contains higher boilinghydrocarbons in the presence greater or less proportions of titanium ofaluminum chlorid to convert the higher chlorid, silicon. chlorid andiron chlorid. To 60 'boilin hydrocarbons into lower boiling hysomeextent these accompany the oily vapors drocar ons, passing the vaporsproduced toproduced when the aluminum chlorid isused gether with anyhydrochloric .acid which for convertin higher boiling hydrocarbons 1 maybe produced to condensing means, conmtolower. boiling hydrocarbons.

tacting the said vapors with sufiicient water It "is the object of thepresent invention 65 to condense the major portion of them and toobviate dangers of corrosion arising from to dissolve the-hydrochloricacid and delivthese causes. I have discovered that the ering the water,hydrochloric acid solution coils of the final water cooled condenser canHand condensed vapors below the surface of be completely protectedagainst entrance of a column of water and allowing gravital hydrochloricacid vapors or of any substan- 7 separation of the condensedhydrsmgrbons tial amount of chlorids, regardless ofthe and water whilewithdrawing the con ensed character of the aluminum chloriddistillahydrocarbons and maintaining the level of tion or of theparticular grade of chlorid the column of water substantially constantused, by condensing some or most of the oily by continuous withdrawal ofa portion vapors produced in aluminum chlorid dis- 7 thereof; all asmore fully hereinafter set tillation through the agency of water, and

- forth and as claimed. I advantageously do this in a tower; pass- .Inthe art of distilling and converting peing the oily vapors which containsmall 5- troleum hydrocarbons with the aid of aluamounts of chlorideincluding hydrogen minium chlorid, several different methods chlorid, toa tower and in the tower sprayhave been proposed and used. In one suching these vaporswith sufiicient water to conmethod reflux condensers areemployed in dense most of them and to dissolve chlorids T1 the vaporline between the still and the and hydrochloric acid. The water used,the

final water cooled condensers so that there hydrochloric acid solutionand the condenis refluxed back to, the still condensed alusate from thevapors together with any minum chlorid or aluminum chlorid-hysludgeformed from the chlorids, and any drocarbon compounds together withhigher other solid product are delivered below the t boiling oils. Thismethod of distillation has level of a column of water maintained inthe35 many advantages, among them being the tower and the condensed oil isallowed to vpossibility of preventing clogging of the rise and iswithdrawn while the column 90.

final water cooled condensers by aluminum level is maintainedsubstantially constant by chlorid carried over. But as the highboilcontinuous withdrawal of water at a lowing oil operated upon issometimes not abso point. The accumulated sludge is with- 40 lutely dryand may contain oxygen in other drawn from time to tlme.

forms, there will often be a formation of In the accompanying drawings.showing '95 hydrochloric acid vapors which will go forone form ofapparatus suitable for the perward to the final condenser. formance ofmy process,

Under some conditions in distillation no Fig. 1 is a view partly insection and reflux is used between the still and the final partly inside elevation of a still, the conwater cooled condenser. This beingparticudensing tower and cooling box;

larly so when the distillation is conducted Fig. 2 is a vertical sectionon line 2-2 to obtain a certain character of distillate by of Fig. l-lookingv in the direction of the using a relatively small proportionofaluarrows; 1

50 minum chlorid; and in this case-traces, and Fig.3 is an enlargedhorizontal section sometimes appreciable amounts ofaluminum along line3-3 of Fig. 1; and chlorid, as well as hydrochloric acid vapors,. Fig.415 a segmental side elevation of the '(if the oil contains oxygen or anmoisture) lower portion of the tower looking in the V w o ward to h fiel e an Th d ec n f th arrow ma k a In the drawings,- 1 indicates anordinary type of'still provided withshaft 2 for'the ence of aluminum,chlorid in usual stirring apparatus and having a vapor outlet 3, alldiagrammatically shown. The vapor outlet 3 of the still is, connected tothe tower at 4 to deliver vapors of lower boiling hydrocarbons resultingfrom the distillation of higher boiling hydrocarbons in the presthestill 1. The condensing Y tower comprises a shell 5 of steel or the likeinteriorly lined with acid the distributing delivers the lower proofbricks 6 of silica or the like and is :closed at thetop by cover 7carrying an access manhole 8. At the bottom the tower is iprovided withmanhole and cover 9. Sup 1 ported on the grating 10 are a plurality ofhollow tile 11 and immediately above these is provided a distributingbox 12. Above box'is the outlet 13 of the water pipe 14 arranged todeliver water into the distributing box whence it flows over,

and through the tile past the grating 10 into the lower I rising oilyvapors delivered from the still by means of the vapor liiie 3. The wateris supplied through line 14 in such an amount as to condense and of theoil. Below the vapor line inlet is the funnel 15 supported in the liningat 16 and having a leg depending below the normal level of the water inthe tower. This funnel collects above, equalizing pipe 19 is provided.Any" vapors or non-condensible gases which escape past the water spray.may enter this pipe atvthe top and ared'eliveredto the cooling coil.

, Should there be'slight pressure in the other direction these vapors orgases would flow upwardly through the e ualizin i e 19" and would be q gp p carried down by the water spray. 4 e The volume of water in thetower is I kept substantially constant by withdrawal through the pipe 20in communication with portion of the tower through'line 22. Thispiperises upwardly outside the tower to a point past the normal water levelin the tower and ,'as shown, terminates outside the tower at 23 andat apoint approxi-' niatel level with the vapor inlet and with 'open p torevent vacuum formation. At a point slig tly below the oil'outlet 18Qabranch pipe 24' attached to the, withdrawal pipe 20 carries water fromsuch ipe to the conduit 25 leading to the sewer; between the conduit 25and the portion of the tower against theibe wash down the bulk of vaporsThe oil and water separate, the oil (not shown) in the cooling water isconstantly removed from a lower referablyportion of the column pipe 24is the funnel-hke enlargement 26. The end of the 'point'.

the aluminum chlorid is carried down by the water and oxids, andhydrates are formed and if there is any titanium chlorid in the aluminumchloridfthis will also be scrubbed out in oxidized form so that unlesssome means for withdrawing these sludges is pro vided, the line 20 islikely to become clogged and the condenser fail to .work.' Ferricchlorid remains in solution to some extent. Silicon chlorid, gives solidsilica.

If for any reason, the flow of water should obstructed or the watershould notbe carried away at a sufliciently rapid rate to compensate forthe introduction of the water or, if for any reason, water shouldaccumulate in the upper or vapor space in the tower, means are providedfor immediately. causing an overflow. The safety overflow arrangementcomprises the pipe 27 in communication with the tower at a relativelylow point' as at 28 below the level of the water,'and'in communicationwith the'tower at'a relatively high point as at 29 above the vaporinlet. In communication with this pipe 27 at 30 is the flow arrangementprevents flow of water to the still should the water over flow 20 or theline 18 become clogged. The vapor line 3 BXttiildS to a higher levelthanpipe 29 as at It is believed the operation of the appai'atus is obviousfrom the foregoing.

- ,The higher boiling hydrocarbons are.distilled in the presence ofaluminum chlorid in still 1 while the stirring apparatus is 160 waterleg 31 terminating at a level slightly below the connection 29. Thissafety overoperated and oily vapors carrying traces,

or a little more than traces, of titanium, iron and' aluminuin chlorid,etc. and of hydrochloric-ac'id vapors. are carried by.-means of vaporline 3 to the tower 5." Water is introduced to'the tower'through line 14and the ascending vapors are scrubbed bymeans of the descending water.Oil and 'water separate in thetower and the outflow' of water throughline 20 is so regulated that the oil level is. maintained at the oiloutlet 18. scrubbed, washed and separated oil is constantly delivered tothe cooling worms box 17 .while the and pipe 24 connected through theequalizer pipe 19. Vapors coming from the still are sealed againstdirect communication with the pipe 18 by means of the funnel 15.

Ordinarily the temperature of the oil and .Water at the point ofseparation is from 150 to 200*? F.

and any iron, titanium, sillcon and alum1-v All the hydrochloric acidnum chlorids or oxids are removed, as well as other impurities and purelower boiling hydrocarbons are collected in the cooling worm which isthus protected against corrosion and fouling.

What I claim is a 1. In the process of distilling higher boilinghydrocarbons with aluminum chlorid to produce lower boilinghydrocarbons, the step which consists in condensing thepro duced oilyvapors by means of water contacted with them and removing any chlorids,hydrochloric acid and other foreign matters from the vapors by means ofsuch water.

2. The process of converting higher boiling petroleum hydrocarbons intolower boiling petroleum hydrocarbons which comprises distilling thehigher boiling hydrocarbons in the presence of aluminum chlorid andpassing the vapors, together with any hydrochloricacid produced, to ascrubbing device holding a column of water, contacting the vapors in thescrubbing device with sufficient water added above the column tocondense hydrocarbon vapors and to dissolve any hydrochloric acid whilecleaning such vapors of chlorids and other impurities, delivering thewater, the hydrochloric acid solution and condensed vapors, as well asseparated impurities, below the level of the column of water andallowing gravital separation of the condensed hydrocarbons and thewater, withdrawing the condensed hy-- drocarbons, maintaining the columnof water substantially constant by continuous withdrawal of a portionthereof. and removlng from the column of water all solid collectedUncondensed gases and vapors' sludges, such as products formed from thechlorids in the vapors. 1

f 3. The process of condensing vapors of hydrocarbons produced by analuminum chlorid distillation, which comprises scrubbing and condensingsuch vapors with water, delivering all condensed matters to a column ofwater, allowing graVital-separation of the oiland water and removing theoil from the top. of the column, while constantly withdrawing Watcr fromthe bottom of the column and removing at a low point in the column ofwater from time to time accumulated sludge occasioned by solids comingfrom the vapors.

4. The process of purifying and condensing vapors of petroleumhydrocarbons ,produced by distillation with aluminum chlorid made frombauxite, which comprises scrub-. bing and condensing such vapors withwater to remove chlorids accompanying them, de- 3 liveringthe productsof such scrubbing, including condensed oil, to a column of water,removing the condensed oil from the .top' thereof, and drawing off froma low point of said column the solid products formed by the chloridsremoved from the vapors by means of the water.

5. The process of converting higher boiling hydrocarbons into lowerboiling hydrocarbons. which I ,comprises distilling the higher boilinghydrocarbons in the presence of aluminum chlorid, passing the vapors, together with any hydrochloric acid produced, to a'tower containing water,contacting the vapors and the hydrochloric acid with sufficient addedwater to condense the vapors and dissolve the hydrochloric acid,delivering the water, hydrochloric acid solution and condensed vaporsbelow the column of water and allowing gravital separation of thecondensed hydrocarbons and water, withdrawing the condensedhydrocarbons, and maintaining the level of the column of 10 watersubstantially constant by continuous withdrawal of a proportion thereof.

6. In the production of oily distillate from high boiling hydrocarbonsby aluminum chlorid, the process of eliminating chlorids 1 andhydrochloric acid from such distillates which comprises scrubbing thedistillation vapors immediately after their production with water priorto condensation.

vIn testimony whereof, I have hereunto 11 aiiixed my signature.

CHARLES B/BUERGER.

